1. Field of the Invention
The present invention relates to a manufacturing method of a semiconductor device and a substrate processing apparatus in which a thin film is formed over a substrate.
2. Description of the Related Art
As one of semiconductor manufacturing steps, there is a CVD (Chemical Vapor Deposition) step in which a predetermined film-forming process is applied to a surface of a substrate (a substrate to be processed formed on a base that is a silicon wafer, glass, or the like on which a fine electric circuit pattern is formed). In this step, the substrate is mounted in an airtight reaction chamber and heated by a heating unit provided in the chamber, and chemical reaction is caused while a source gas is being introduced onto the substrate, thereby forming a thin film uniformly on the fine electric circuit pattern formed on the substrate. In such a reaction chamber, a thin film is also formed on components other than the substrate. Such a thin film will be hereinafter called a built-up film. In a CVD apparatus shown in FIG. 6, a showerhead 6 and a susceptor 2 are provided in a reaction chamber 1, and a substrate 4 is mounted on the susceptor 2. A source gas is introduced into the reaction chamber 1 through a source supply pipe 5 connected to the showerhead 6 and supplied onto the substrate 4 via a number of holes 8 provided in the showerhead 6. The gas supplied onto the substrate 4 is exhausted through an exhaust pipe 7. The substrate 4 is heated by a heater 3 provided under the susceptor 2. Note that a built-up film is accumulated and deposited on components around the substrate such as the showerhead 6, the susceptor 2, and so on in accordance with increase in the number of substrates processed, in other words, increase in the number of processing times.
As such a CVD apparatus, there is a CVD apparatus that uses a MOCYD (Metal Organic Chemical Vapor Deposition) method with which an amorphous HfO2 film and an amorphous Hf silicate film (they are hereinafter abbreviated to an a-HfO film), an amorphous Ta2O5 film (it is hereinafter abbreviated to an a-TaO film), and an amorphous Ru film and an amorphous RuO2 film (they are hereinafter abbreviated to an a-Ru film) can be formed by using an organic chemical material as a film-forming source.
As the film-forming source, Hf[OC(CH3)3]4 (hereinafter, abbreviated to Hfxe2x80x94(OtBu)4), Hf[OC(CH3)2CH2OCH3]4 (hereinafter, abbreviated to Hf-(MMP)4 (here, MMP: 1methoxy-2-methyl-2-propoxy)), Hf[Oxe2x80x94Sixe2x80x94(CH3)]4 (hereinafter, abbreviated to Hfxe2x80x94(OSi)4), and the like are used for forming the a-HfO film; Ta(OC2H5)5 (hereinafter, abbreviated to PETa) and the like are used for forming the a-TaO film; and Ru(CH2C5H4)2 (hereinafter, abbreviated to Ru(EtCp)2) and the like are used for forming the a-Ru film.
Among them, many organic materials, for example, Hfxe2x80x94(OtBu)4, Hf-(MMP)4, PETa, Ru(EtCp)2, and so on are in liquid phase at normal temperatures and pressures. Therefore, these organic liquid sources are heated and thus transformed to gas by vapor pressure for utilization.
[Patent Document 1]
Japanese Patent Laid-open No. 2001-237397 (pages 4 to 7, FIG. 5)
[Patent Document 2]
Japanese Patent Laid-open No. 2000-235962 (page 3, FIG. 1)
[Patent Document 3]
Japanese Patent Laid-open No. Hei 11-217672 (pages 6 to 8, FIG. 1)
The built-up film is constantly deposited in the reaction chamber of the MOCVD apparatus as described above, and H2, H2O, CO, CO2, CH4, and the like are constantly coming out as eliminated gases from this built-up film. This is because a thin film such as the a-HfO film, a-TaO-film, and a-Ru film deposited with good coverage by a conventional MOCVD method contains a large amount of C, H, OH, and the like as impurities, H2O among these eliminated gases gives an extremely significant influence to the substrate to be processed. For example, when the substrate to be processed is an Si substrate, H2O modifies the surface of the substrate to a low quality oxide or hydroxide such as Sixe2x80x94OH or SiOx(x less than 2), and consequently, turns out to be a factor of greatly lowering the properties of a semiconductor device that is an end product, which poses a big problem.
Presently, in order to avoid such a serious situation, an enormous amount of labor and expenses are spent for alleviating the adverse effect of H2O in the MOCVD reaction chamber and the adverse effect of H2O which occurs due to elimination from Xxe2x80x94OH (Xxe2x95x90Hf, Zr, Ta, Ru, or the like) contained in a MOCVD thin film by, for example, subjecting the surface of the Si substrate to a substrate surface modifying process such as nitridation, oxidation, oxynitridation, or CVD-TIN process in advance to form a barrier layer against H2O.
The thin film deposited using the MOCVD method as described above has a disadvantage that flatness of a film surface is difficult to obtain. Especially, in the MOCVD method in the case when the thin film deposit rate is determined by surface reaction rate controlling conditions, the abovementioned problem is obvious. It is known that the thin film starts to be deposited on the substrate surface with a certain time lag in the surface reaction rate controlling conditions. This time lag is called an incubation time. During this incubation time, there is a nucleation process in which an island-shaped deposition is made on the substrate, and it is thought that the thin film loses its flatness due to the formation of irregularities in this nucleation process.
Such lack in flatness on the thin film surface becomes a cause of lowering reliability of a semiconductor device product that is an end product, and is becoming a significant problem in accordance with downsizing of the device.
It is an object of the present invention to provide a manufacturing method of a semiconductor device and a substrate processing apparatus capable of effectively and efficiently inhibiting the influence of an eliminated gas from a built-up film deposited in a reaction chamber of a MOCVD apparatus and reducing an incubation time to improve flatness of a thin film. It is another object of the present invention to provide a manufacturing method of a semiconductor device and a substrate processing apparatus capable of greatly saving an enormous amount of labor and expenses which have been conventionally spent for improving the aforesaid serious situation and simplifying a substrate surface modifying process so as to concentrate this process in a MOCVD apparatus, thereby greatly reducing production cost. It is still another object of the present invention to provide a manufacturing method of a semiconductor device and a substrate processing apparatus capable of inhibiting the influence of an eliminated gas from a built-up film deposited in a reaction chamber of a MOCVD apparatus and improving flatness of a thin film, without lowering productivity.
A first invention is a manufacturing method of a semiconductor device which is characterized in that it includes: a preprocess step of performing a preprocess to a substrate from which a natural oxide film is removed; and a film-forming step, subsequent to the preprocess step, of forming a metal thin film or a metal oxide thin film over the substrate, the preprocess step including a nitrogen preprocess step of activating a nitrogen (N)-containing gas and supplying the activated nitrogen-containing gas to the substrate and an oxygen preprocess step of activating an oxygen (O)-containing gas and supplying the activated oxygen-containing gas to the substrate. The preprocess step makes it possible to effectively and efficiently inhibit the influence of an eliminated gas from a built-up film and reduce an incubation time to improve flatness of the film formed in the film-forming step. Moreover, since the preprocess step includes the nitrogen preprocess step and the oxygen preprocess step, the quality of a semiconductor device can be enhanced compared with that when only the nitrogen preprocess or the oxygen preprocess is independently performed. To be more specific, in the preprocess including only the nitrogen preprocess (for example, a later-described RPN process), though leak current can be inhibited, an interface defect density of an end device increases to degenerate electric parameters such as flat band voltage Vfb and motility xcexc. In the preprocess including only the oxygen preprocess (for example, a later-described RPO process), though the interface defect of the end device can be reduced, the limit of downsizing the device is lowered due to the increase in the leak current. In contrast, the present invention has both the nitrogen preprocess and the oxygen preprocess so that the abovementioned disadvantages in the independent execution of each of the processes can be mutually complemented. The nitrogen preprocess step and the oxygen preprocess step are preferably performed in this order since the effect of repairing the interface defect in the latter oxygen preprocess step is obtainable even if the interface defect occurs in the former nitrogen preprocess step.
A second invention is a manufacturing method of a semiconductor device, characterized in that it includes: a preprocess step of performing a preprocess to a substrate; and a film-forming step, subsequent to the preprocess step, of forming a metal thin film or a metal oxide thin film over the substrate, the preprocess step including a hydrogen preprocess step of activating a hydrogen (H)-containing gas and supplying the activated hydrogen-containing gas to the substrate or a chlorine preprocess step of activating a chlorine (Cl)-containing gas and supplying the activated chlorine-containing gas to the substrate, a nitrogen preprocess step of activating a nitrogen (N)-containing gas and supplying the activated nitrogen-containing gas to the substrate, and an oxygen preprocess step of activating an oxygen (O)-containing gas and supplying the activated oxygen-containing gas to the substrate; and that the preprocess step and the film-forming step are performed in one reaction chamber. A conventional preprocess for a substrate to be processed has a disadvantage that the substrate is contaminated while it is conveyed since the preprocess is performed in a different reaction chamber from that for a film-forming process. On the other hand, according to the present invention, the same reaction chamber is used for the preprocess step and the film-forming step so that the film-forming step can be performed successively immediately after the preprocess step and a substrate conveying step can be omitted, which makes it possible to prevent the substrate surface cleaned in the preprocess step from being re-contaminated while it is conveyed. In addition, production cost can be greatly reduced. Further, the execution of the preprocess step and the film-forming step in the same reaction chamber allows the conventional substrate heating time in the reaction chamber to be utilized for the preprocess, This enables efficient execution of these two processes in one reaction chamber. Moreover, since the preprocess step and the film-forming step are performed in the same reaction chamber, the film can be formed immediately after the preprocess for the substrate, which enables the formation of a high-quality interface layer.
A third invention is a manufacturing method of a semiconductor device characterized in that it includes: a preprocess step of activating a gas and supplying the activated gas to a substrate; and a film-forming step, subsequent to the preprocess step, of forming a metal thin film or a metal oxide thin film over the substrate, and that the preprocess step is performed during substrate temperature increase for raising a substrate temperature up to a film-forming temperature before a source gas is supplied in the film-forming step. When the preprocess step is performed during the temperature increase for raising the substrate temperature up to the film-forming temperature, the influence of the eliminated gas from the built-up film is inhibited and the incubation time is reduced to improve flatness of the film formed in the film-forming, without lowering productivity. In addition, the activated gas is used in the preprocess, and reliable preprocess is possible even during the temperature increase in which the temperature has not reached a processing temperature, since activation energy is larger than thermal energy.
A fourth invention is a manufacturing method of a semiconductor device characterized in that, in the first invention, in the film-forming step, a source gas supply step of supplying a source gas to the substrate and an activated gas supply step of activating a gas and supplying the activated gas after the source gas supply step are repeated a plurality of times, thereby forming a thin film having a desired film thickness. Since the source gas supply step and the activated gas supply step are repeated a plurality of times, a removal amount of impurities such as C and H in the formed film can be increased. Moreover, the repeat of the source gas supply step and the activated gas supply step (especially, the activated gas supply step) also has an effect of inhibiting the influence of the eliminated gas from the built-up film deposited in the reaction chamber.
A fifth invention is a substrate processing apparatus characterized in that it includes; a reaction chamber in which a substrate is processed; a heater heating the substrate in the reaction chamber; a source gas supply port through which a source gas is supplied into the reaction chamber; a gas activating unit activating each of a hydrogen- or chlorine-containing gas, a nitrogen-containing gas, and an oxygen-containing gas; an activated gas supply port through which the gases activated in the gas activating unit are supplied into the reaction chamber; and a control unit performing such a control operation that the activated gases are successively supplied one by one to the substrate in the reaction chamber while a temperature of the substrate heated by the heater is lower than a film-forming temperature, and performing such a control operation that the source gas used for forming a film on the substrate in the reaction chamber is supplied after the substrate temperature is raised up to the film-forming temperature and thereafter, the activated gases are supplied to the substrate.
A sixth invention is a manufacturing method of a semiconductor device characterized in that, in the first invention, the preprocess step further includes, prior to the nitrogen preprocess step and the oxygen preprocess step, a hydrogen preprocess step of activating a hydrogen (H)-containing gas and supplying the activated hydrogen-containing gas to the substrate or a chlorine preprocess step of activating a chlorine (Cl)-containing gas and supplying the activated chlorine-containing gas to the substrate. The hydrogen preprocess or the chlorine preprocess is further performed so that the substrate surface is further cleaned and thus can have a more active surface condition, thereby enabling better modification of the substrate surface in the preprocess.
A seventh invention is a manufacturing method of a semiconductor device characterized in that, in the first invention, the preprocess step and the film-forming step are performed in one reaction chamber.
An eighth invention is a manufacturing method of a semiconductor device characterized in that, in the second invention, the nitrogen preprocess step and the oxygen preprocess step are performed after the hydrogen preprocess step or the chlorine preprocess step. This processing order of the hydrogen preprocess step or the chlorine preprocess step followed by the nitrogen preprocess step and the oxygen preprocess step increases the effect of the preprocess.
A ninth invention is a manufacturing method of a semiconductor device characterized in that, in the second invention, the preprocess step is performed during a substrate temperature increase for raising a substrate temperature up to a film-forming temperature, before the source gas is supplied in the film-forming step.
A tenth invention is a manufacturing method of a semiconductor device characterized in that, in the third invention, the preprocess step includes a nitrogen preprocess step of activating a nitrogen (N)-containing gas and supplying the activated nitrogen-containing gas and an oxygen preprocess step of activating an oxygen (O)-containing gas and supplying the activated oxygen-containing gas.
An eleventh invention is a manufacturing method of a semiconductor device characterized in that, in the third invention, the preprocess step includes a hydrogen preprocess step of activating a hydrogen (H)-containing gas and supplying the activated hydrogen-containing gas or a chlorine preprocess step of activating a chlorine (Cl)-containing gas and supplying the activated chlorine-containing gas, a nitrogen preprocess step of activating a nitrogen (N)-containing gas and supplying the activated nitrogen-containing gas, and an oxygen preprocess step of activating an oxygen (O)-containing gas and supplying the activated oxygen-containing gas.
A twelfth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first invention to the eleventh invention, the gas is activated in the preprocess step by using plasma. The use of the gas activated by using the plasma can effectively and efficiently inhibit the influence of the eliminated gas from the built-up film, and reduce the incubation time to improve flatness of the thin film.
A thirteenth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to twelfth inventions, the gas is activated in the preprocess step by using plasma in a remote plasma unit provided outside the reaction chamber in which the substrate is processed. The use of the gas activated in the remote plasma can further inhibit the influence of the eliminated gas from the built-up film effectively and efficiently, and reduce the incubation time to improve flatness of the thin film.
A fourteenth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to thirteenth inventions, the hydrogen preprocess step is a remote plasma hydrogenation process in which the hydrogen-containing gas is activated in a remote plasma unit and the activated hydrogen-containing gas is supplied to the substrate to hydrogenate a surface of the substrate, the chlorine preprocess step is a remote plasma chlorination process in which the chlorine-containing gas is activated in the remote plasma unit and the activated chlorine-containing gas is supplied to the substrate to chlorinate the surface of the substrate, the nitrogen preprocess step is a remote plasma nitridation process in which the nitrogen-containing gas is activated in the remote plasma unit and the activated nitrogen-containing gas is supplied to the substrate to nitride the surface of the substrate, and the oxygen preprocess step is a remote plasma oxidation process in which the oxygen-containing gas is activated in the remote plasma unit and the activated oxygen-containing gas is supplied to the substrate to oxidize the surface of the substrate.
A fifteenth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to fourteenth inventions, a source gas used in the film-forming step is an organic source gas. The use of the organic source gas in the case when flatness of the film surface is difficult to obtain and the problem of the eliminated gas occurs is especially advantageous since it can improve flatness and inhibit the influence of the eliminated gas effectively and efficiently.
A sixteenth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to fifteenth inventions, the film-forming step has a source gas supply step of supplying a source gas to the substrate and an activated gas supply step, subsequent to the source gas supply step, of activating a gas and supplying the activated gas to the substrate, the source gas used in the film-forming step is a gas obtained by vaporizing Hf[OC(CH3)2CH2OCH3]4, and the formed thin film is a film including Hf.
A seventeenth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to fifteenth inventions, the film-forming step has a source gas supply step of supplying a source gas to the substrate and an activated gas supply step, subsequent to the source gas supply step, of activating a gas and supplying the activated gas to the substrate, the source gas used in the film-forming step is a gas obtained by vaporizing Ta(OC2H5)5, and the formed thin film is a film including Ta.
An eighteenth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to fifteenth inventions, the film-forming step has a source gas supply step of supplying a source gas to the substrate and an activated gas supply step, subsequent to the source gas supply step, of activating a gas and supplying the activated gas to the substrate, the source gas used in the film-forming step is a gas obtained by vaporizing any one of Ru(C2H5C5H4)2 (bisethylcyclopentadienylruthenium), Ru(C5H5)(C4H9C5H4) (buthylruthenocene), Ru[CH3COCHCO(CH2)3CH3]3 (tris-2,4octanedionatoruthenium), Ru(C2H5C5H4)((CH3)C5H5) (2,4dimethylpentadienylethylcyclopentadienylruthenium, and Ru(C7H8)(C7H11O2), and the formed film is a film including Ru.
A nineteenth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to fifteenth inventions, the film-forming step has a source gas supply step of supplying a source gas to the substrate and an activated gas supply step, subsequent to the source gas supply step, of activating a gas and supplying the activated gas to the substrate, the source gas used in the film-forming step is a gas obtained by vaporizing any one of Ti[(OCH(CH3)2)]4, Ti(OCH2CH3)4, Ti[N(CH3)2]4, and Ti[N(CH3CH2)2]4, and the formed film is a film including Ti.
A twentieth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to nineteenth inventions, the film-forming step has a source gas supply step of supplying a source gas to the substrate and an activated gas supply step, subsequent to the source gas supply step, of activating a gas and supplying the activated gas to the substrate, and, in the activated gas supply step, at least one kind of gas selected from a group consisting of O2, N2O, NO, Ar, H2, N2, and NH3 is activated by plasma and the activated gas is supplied.
A twenty-first invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to twentieth inventions, a nitrogen preprocess step of activating a nitrogen (N) containing gas and supplying the nitrogen-containing gas and an oxygen preprocess step of activating an oxygen (O)-containing gas and supplying the oxygen-containing gas are repeated a plurality of times in the preprocess step. The preprocess step includes the nitrogen preprocess step and the oxygen preprocess step so that the, aforesaid disadvantages in the case of the independent execution of each of the processes can be mutually complemented, and especially when the nitrogen preprocess step and the oxygen preprocess step are performed in this order, the effect of repairing the interface defect in the latter oxygen preprocess step is obtainable even if the interface defect occurs in the former nitrogen preprocess step. In addition, these nitrogen preprocess step and the oxygen preprocess step are repeated a plurality of times so that the abovementioned effect obtained by one repeat can be further enhanced.
A twenty-second invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the first to twenty-first inventions, at least during the preprocess step, the substrate is rotated. It is preferable that the substrate is rotated at least during the preprocess step since a uniform modifying process over the surface of the substrate is made possible. Incidentally, it is preferable that the substrate is rotated both during the preprocess step and during the film-forming step, and, it is more preferable that the substrate is rotated during all the steps of the substrate surface treatment step, the preprocess step, and the film-forming step.
A twenty-third invention is a manufacturing method of a semiconductor device characterized in that it includes a preprocess step of successively supplying plural kinds of radicals selected from a hydrogen radical, a nitrogen radical, and an oxygen radical to a substrate one by one and a film-forming step of forming a metal thin film or a metal oxide thin film in an amorphous state over the substrate having undergone the preprocess step. Since the preprocess step of supplying the plural kinds of radicals successively to the substrate one by one is performed before the film-forming step, it is possible to inhibit the influence of the eliminated gas from the built-up film deposited in the reaction chamber of the MOCVD apparatus effectively and efficiently, and reduce the incubation time to improve flatness of the thin film. Further, the substrate surface modifying process as the preprocess step can be simplified to greatly save an enormous amount of labor and expenses which have been conventionally spent for a countermeasure against the eliminated gas from the built-up film, and the substrate surface modifying process can be concentrated in the MOCVD apparatus to greatly reduce production cost.
A twenty-fourth invention is a manufacturing method of a semiconductor device characterized in that, in the twenty-third invention, the preprocess step and the film-forming step are performed in one reaction chamber.
A twenty-fifth invention is a manufacturing method of a semiconductor device characterized in that, in the twenty-third or twenty-fourth invention, the film-forming step has a source gas supply step of supplying a source gas to the substrate and a radical supply step of supplying one kind of radical selected from a hydrogen radical, a nitrogen radical, and an oxygen radical after the source gas supply step, and the source gas supply step and the radical supply step are repeated a plurality of times, thereby forming the thin film having a desired film thickness. Since the source gas supply step and the radical supply step are repeated a plurality of times, the thin film having a predetermined film thickness can be formed and a removal amount of impurities such as C and H in the formed film can be increased. Moreover, the repeat of the source gas supply step and the radical supply step (especially, the radical supply step) also has an effect of inhibiting the influence of the eliminated gas from the built-up film deposited in the reaction chamber of the MOCVD apparatus.
A twenty-sixth invention is a manufacturing method of a semiconductor device characterized in that, in the twenty-fourth or twenty-fifth invention, the preprocess step is performed during a substrate temperature increase for raising a substrate temperature up to a film-forming temperature, before the source gas supply in the film-forming step.
A twenty-seventh invention is a substrate processing apparatus characterized in that it includes: a reaction chamber in which a substrate is processed; a heater heating the substrate in the reaction chamber; a source gas supply port through which a source gas is supplied into the reaction chamber; a radical generating unit capable of generating plural kinds of radicals selected from a hydrogen radical, a nitrogen radical, and an oxygen radical; a radical supply port through which the radical generated in the radical generating unit is supplied into the reaction chamber; and a control unit performing such a control operation that the plural kinds of radicals are successively supplied to the substrate in the reaction chamber one by one, while a temperature of the substrate heated by the heater is lower than a film-forming temperature, and performing such a control operation that the source gas is supplied to the substrate in the reaction chamber after the substrate temperature is raised up to the film-forming temperature and thereafter, one kind of radical selected from the hydrogen radical, the nitrogen radical, and the oxygen radical is supplied to the substrate.
The control unit is provided that performs such a control operation that the substrate is heated by the heater, the plural kinds of radicals selected from the hydrogen radical, the nitrogen radical, and the oxygen radical are successively supplied to the substrate in the reaction chamber one by one while the substrate temperature is lower than the film-forming temperature, and such a control operation that the source gas is supplied to the substrate in the reaction chamber after the substrate temperature is raised up to the film-forming temperature and thereafter, one kind of radical selected from the hydrogen radical, the nitrogen radical, and the oxygen radical is supplied, so that the manufacturing method of the semiconductor device according to the twenty-fourth invention can be easily executed. Incidentally, when a control unit is further provided that performs such a control operation that the source gas is supplied to the substrate in the reaction chamber after the substrate temperature is raised up to the film-forming temperature, thereafter one kind of radical selected from the hydrogen radical, the nitrogen radical, and the oxygen radical is supplied, and the source gas supply and the radical supply are repeated a plurality of times, the manufacturing method of the semiconductor device according to the twenty-fifth invention can be easily executed. Incidentally, when a control unit is further provided that performs such a control operation that the plural kinds of radicals are supplied successively to the substrate in the reaction chamber one by one during the substrate temperature increase, the manufacturing method of the semiconductor device according to the twenty-sixth invention can be easily executed.
A twenty-eighth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the twenty-third to twenty-seventh inventions, the plural kinds of radicals are generated in such a manner that plural kinds of gases selected from a gas including hydrogen atoms, a gas including nitrogen atoms, and a gas including oxygen atoms are activated using plasma in a remote plasma unit provided outside the reaction chamber in which the substrate is processed, The use of especially the radicals activated in the remote plasma, among radicals, can inhibit the influence of the eliminated gas from the built-up film effectively and efficiently, and reduce the incubation time to improve flatness of the thin film.
A twenty-ninth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the twenty-eighth invention, the preprocess step is a process in which plural kinds of remote plasma processes are applied to the substrate successively one by one, the plural kinds of remote plasma processes being selected from a remote plasma hydrogenation process in which a substrate surface is hydrogenated using the hydrogen radical generated by activating a hydrogen-containing gas in the remote plasma unit, a remote plasma nitridation process in which the substrate surface is nitrided using the nitrogen radical generated by activating a nitrogen-containing gas in the remote plasma unit, and a remote plasma oxidation process in which the substrate surface is oxidized using the oxygen radical generated by activating an oxygen-containing gas in the remote plasma unit. Especially, the plural kinds of processes, among remote plasma processes, selected from the remote plasma hydrogenation process, the remote plasma nitridation process, and the remote plasma oxidation process are performed successively, so that the influence of the eliminated gas from the built-up film can be inhibited effectively and efficiently, and the incubation time can be reduced to improve flatness of the thin film.
A thirtieth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the twenty-ninth invention, the preprocess step is a process in which the remote plasma hydrogenation process, the remote plasma nitridation process, and the remote plasma oxidation process are performed successively in this order. Especially when the remote plasma hydrogenation process, the remote plasma nitridation process, and the remote plasma oxidation process are all performed successively in this order, the abovementioned effects are prominent.
A thirty-first invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the twenty-third to thirtieth inventions, the source gas used in the film-forming step is an organic source gas.
A thirty-second invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the thirty-first invention, the film-forming step has a source gas supply step of supplying a source gas to the substrate and a radical supply step of supplying a radical after the source gas is supplied, the source gas used in the film-forming step is a gas obtained by vaporizing Hf[OC(CH3)2CH2OCH3]4, the radical supplied thereafter is an oxygen radical, and the formed thin film is a HfO2 film.
A thirty-third invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the thirty-first invention, the film-forming step has a source gas supply step of supplying a source gas to the substrate and a radical supply step of supplying a radical after the source gas is supplied, the source gas used in the film-forming step is a gas obtained by vaporizing Ta(OC5H5)5, the radical supplied thereafter is an oxygen radical, and the formed thin film is a Ta2O5 film.
A thirty-fourth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the thirty-first invention, the film-forming step has a source gas supply step of supplying a source gas to the substrate and a radical supply step of supplying a radical after the source gas is supplied, the source gas used in the film-forming step is a gas obtained by vaporizing Ru(C2H5C5H4)2, the radical supplied thereafter is a hydrogen radical or an oxygen radical, and the formed thin film is an Ru film or an RuO2 film.
A thirty-fifth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the thirty-first invention, the film-forming step has a source gas supply step of supplying a source gas to the substrate and a radical supply step of supplying a radical after the source gas is supplied, the source gas used in the film-forming step is a gas obtained by vaporizing Ti(N(CH3)2)4, the radical supplied thereafter is a nitrogen radical, and the formed thin film is a TiN film.
A thirty-sixth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the twenty-third to thirty-fifth inventions, it further includes a substrate surface treatment step of removing a natural oxide film and a contaminant on the substrate surface before the preprocess step.
A thirty-seventh invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the thirty-sixth invention, the substrate surface treatment step, the preprocess step, and the film-forming step are performed in the same reaction chamber.
A thirty-eighth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the thirty-sixth or thirty-seventh invention, the substrate surface treatment step is a remote plasma dry cleaning process of supplying the substrate in the reaction chamber with a radical generated by activating a cleaning gas using plasma in a remote plasma unit provided outside the reaction chamber in which the substrate is processed, thereby removing the natural oxide film formed on the substrate surface or a metal contaminant.
A thirty-ninth invention is a manufacturing method of a semiconductor device or a substrate processing apparatus characterized in that, in the twenty-third to thirty-eighth inventions, the substrate is rotated at least during the preprocess step.